Process for removing acids with an ethylene glycol monoalkylamine ether



L. F. KING ET AL Oct. 18, 1960 PROCESS FOR REMOVING ACIDS WITH ANETHYLENE GLYCOL MONOALKYLAMINE EITHER Filed July 10, 1958 l! I mu 7 m; 2I I on t V m. mwsoh w\u zmE $53 k F mm BM: 5 I I zoFo E mmmzwozoo 85.20%i N mzoN wzjtmm EEBIQ 2238 w n 292 355 $9.6m mm ok M23 @259; m I 22356IE2; w o I 52%; N

Laurence F. King Inventors William H. White United States Patent PROCESSFOR REMOVING ACIDS WITH AN IFEZTI-IgkENE GLYCOL MONOALKYLAMINE LaurenceF. King, Mooretown, Ontario, and William H. White, Calgary, Alberta,Canada, assignors to Esso Research and Engineering Company, acorporation of Delaware Filed July '10, 1958, Ser. No. 747,693

28 Claims. (Cl. 20826'3).

The present invention relates to the upgrading of hydrocarbon oils andmore particularly relates to an improved solvent extraction process forremoving acid oils from petroleum distillates by treating suchdistillates with ethylene glycol monoalkylamine ethers.

This invention is a continuation-in-part of that described in copendingapplication S.N. 618,793, filed on October 29, 1956.

The removal of acid oils from petroleum distillates has long constituteda serious problem in the refining of hydrocarbon oils. Conventionallythese materials, which consist of phenolic compounds such as alkylatedphenols, cresols, xylenols, thiophenols and the like and are unrelatedto organic and inorganic acids, are removed by caustic treating intendedto improve the stability, odor and corrosivity of the distillates. Suchprocesses employing caustic are not entirely satisfactory, however,because of problems in disposing of the resulting spent caustic. Causticconsumed in reactions with acid oils cannot be regenerated byconventional procedures, although mercaptans and other contaminantspresent in spent caustic can be removed by oxidation or similartreatment. As a result, sodium phenolate, sodium thiophenolate andsimilar contaminants derived from the reaction of the caustic with acidoils accumulate in the caustic solution until it loses its effectivenessas an extracting agent and tends to form stable emulsions with the oilbeing treated. At this point it becomes necessary to discard the causticsolution. Because of the voluminous quantities of caustic used fortreating stocks containing acid oils and because of the increasingemphasis placed upon preventing stream pollution, disposal of causticspent in this manner is becoming a serious problem. Much effort has beendirected toward the development of caustic regeneration processes whichwill avoid the necessity for disposing of spent caustic in this mannerbut to date suitable processes have not been developed.

- The present invention provides a new and improved solvent extractionprocess for the removal of acid oils from petroleum distillates whichavoids the use of caustic and the problems arising therefrom. Inaccordance with the invention, it has been discovered that petroleumdistillates substantially free of acid oils and having very low coppernumbers and improved odors can be produced by contacting distillatescontaining acid oils with ethylene glycol monoalkylamine ethers underconditions such that separate extract and raftinate phases are formedand thereafter recovering the hydrocarbons from each phase. It has beenfound that such treatment, in addition to removing acid oils, alsoremoves sulfur compounds from cracked distillates and takes out smallamounts of sludge-inducing nitrogen compounds not removed inconventional solvent extraction processes. The acid oils removed by theethylene glycol monoalkylamine ethers, unlike those'extracted withcaustic, may readily be recovered and further processed for use aschemical byproducts. The ethylene glycol monoalkylamine ethers have asurprisingly high capacity as solvents and may "ice be readilyregenerated to permit their repeated use. The

group and one terminal amino group and have the following generalstructural formula:

HO- CH CH 0) CH NH where x is a digit from 1 to 4' inclusive and y is adigit- The solvents employed in accord-' from 1 to 5 inclusive. ance'with the invention thus include both monoethylene glycol monoalkylamineethers and polyethylene glycol monoalkylamine ethers. Compounds withinthis group are monoethylene glycol monomethylamine ether, monoethyleneglycol monoethylamine ether, monoethylene glycol monopropylamine ether,monoethylene glycol mono butylamine ether, monoethylene glycolmonoamylamine ether, diethylene glycol monomethylamine ether, diethyleneglycol monoethylamine ether, diethylene glycol monopropylamine ether,diethylene glycol monobutyl:

amine ether, diethylene glycol monoamylamine ether,-

triethylene glycol monomethylamine ether, triethylene glycolmonoethylamine ether, triethylene lycol monopropylamine ether,triethylene glycol monobutylamine ether, triethylene glycolmonoamylamine ether, tetraethylene glycol monomethylamine ether,tetraethylene glycol monoethylamine ether, tetraethylene glycolmonopropylamine ether, tetraethylene glycol monobutylamine ether andtetraethylene glycol monoamylamine ether. Of these, monoethylene glycolmonopropylamine ether, diethylene glycol monopropylamine ether, andtriethylene glycol monobutylamine ether have been found particularlyeifective and are therefore preferred for purposes of the invention. 1

The ethylene glycol monoalkylamine ethers which constitute the solventsof the invention are not to be cona fused with glycols which have beenemployed as solvents tive for the removal of acid oils from petroleumdistillates. Such mixtures lack the selectivity necessary to permittheir use for purposes of the invention and in addition are extremelydifficult to handle because the amine compound is ether leached from thesolvent on contact with the hydrocarbon phase or is lost when it isattempted to recover the solvent. The ethylene glycol monoalkylamineethers are thus singularly adapted forextracting acid oils frompetroleum distillates and possess properties which distinguish them fromsolvents employed in thepast.

The ethylene glycol monoalkylamine ethers used in the process of theinvention may be employed in either anhydrous or aqueous form. Aqueoussolvents contain ing from about 1 to 50% water by weight willselectively extract acid oils from the distillates treated without theremoval of aromatics to any appreciable extent. If, however, it isdesired to remove aromatics as well as acid oils, an anhydrous solventmay be employed, in which case an aromatic extract useful as a solventbase, as a fuel constituent, or as a starting material in chemicalsmanufacture can be recovered. In most cases use of the aqueous solventsto permithighly selective extractions of acid oils alone will bepreferred.

' Ethylene glycol monoalkylamine ethers may be employed in accordancewith the invention for removing acid oils from a wide variety of.petroleum distillates including naphthas, middle distillates and gasoils boiling up to about 900 F. Such distillates include fractionsconventionally employed in the manufacture of gasolines, kerosenes,diesel fuels, turbo-jet engine fuels, heating oils, lubricating oils,transformer oils, hydrocarbon solvents and similar products. Thesolvents of the invention are especially attractive for the treatment ofcracked petroleum distillates, since it has been found that they areeffective for the removal of not only acid oils but also sulfurcontaminants from such oils. The process thus provides a method forsimultaneously sweetening and removing acid oils from crackeddistillates.

In carrying out the process of the invention, the oil to be treated andthe ethylene glycol monoalkylamine ether are contacted under conditionsto form separate raffinate and extract phases. Although it is preferredto carry out this contacting in a countercurrent extraction tower fittedwith plates, trays or the like or in one filled with a suitable packingsuch as Raschig rings or stoneware saddles, other conventionalcontacting systems are also applicable. In some cases it may, forexample, be preferred to carry out the contacting in one or moremixer-settler vessels. The contacting temperature employed in carryingout the process may be varied over a considerable range depending uponwhether an aqueous or an anhydrous solvent is employed and furtherdepending upon the extent to which it is desired to extract aromatichydrocarbons from the feed stream. When aqueous ethylene glycolmonoalkylamine ethers are employed and it is desired to effect a highlyselective removal of acid oils alone from the distillate being treated,the contacting temperature will preferably fall in the range betweenabout 60 F. and about 150 F. Use of an aqueous solvent at highertemperatures, between about 150 and about 300 F., results in the removalof both acid oils and aromatics. The anhydrous solvents have been foundeffective between about 60 and 150 F. but may also be used at somewhathigher temperatures. The contacting temperature used will thus normallyrange between about 60 and about 300 F.

The amount of solvent employed in carrying out the process willgenerally range between about 0.1 to about 5.0 volumes per volume of oilto be treated. Variations within this range will depend upon thequantity of aromatic extract which it is desired to recover and theextract purity desired. Solvent-to-feed ratios of from about 0.5 toabout 2 volumes per volume have been found to be particularly effectiveand are preferred.

The ethylene glycol monoalkylamine ethers employed as solvents inaccordance with the invention may be recovered from the extract andraflinate phases formed in treating petroleum distillates by waterwashing, fractionation or other methods conventionally employed insolvent extraction processes. It is generally preferred to water washboth phases in order to separate the hydrocarbons from the solvent andthen remove the water added by flashing it at a temperature betweenabout 220 F. and about 350 F. At these temperatures the solvents arestable and a highly effective separation can be made. The solvents canbe periodically or continuously regenerated by vacuum distillation,providing, of course, that there is a sufficient difference between theboiling point of the ethylene glycol monoalkylamine ether used and theinitial or final boiling point of the distillate treated. In order toprovide such a difference in boiling points, it is generally preferredto employ the polyethylene glycol monoalkylamine ethers when treatingnaphthas and to use the monoethylene glycol monoalkylamine ethers forthe treating of middle distillates, gas oils and the like.

Other methods for removing impurities from the spent solvents, the useof a second solvent to extract impurities from the ethers, for example,may also be used.

The exact nature and objects of the invention can be more clearlyunderstood by referring to the following detailed description of apreferred embodiment of the process and to the accompanying drawingillustrating that preferred embodiment.

Referring to the drawing, a petroleum distillate containing acid oilsand boiling in the range between about F. and about 900 F., a crackedgas oil boiling between 450 F. and 620 F. for example, is introducedinto the system through line 1 and into extraction tower 2. Tower 2 ispreferably a countercurrent liquid-liquid extraction tower adapted topromote intimate contact between the gas oil feed stream and ananhydrous monoethylene glycol monopropylamine ether stream introducedinto the upper portion of the tower through line 3. It is preferred thatthe tower be fitted with trays of the type conventionally employed inphenol extraction and similar liquid-liquid extraction processes. Thegas oil and monoethylene glycol monopropylamine ether streams areintroduced into tower 2 at rates to give a solvent to feed ratio ofabout 1 to l. The gas oil and ether streams flow countercurrently to oneanother within the contacting tower. A rafi'mate phase consistingessentially of gas oil free of acid oils and having entrained anddissolved therein a small amount of ethylene glycol monopropylamineether is withdrawn overhead from tower 2 through line 4 and passed intowashing zone 5. A stream of water is introduced into the upper part ofthe washing zone through line 6 in order to wash solvent from the oil.Essentially solvent-free product oil is withdrawn from the washing zonethrough line 7. This stream is free of acid oils, has a substantiallybetter odor than the feed stream, is doctor pass, and contains fewersaromatics than did the gas oil feed. The water used in washing therafiinate is withdrawn from vessel 5 through line 8.

An extract stream consisting of monoethylene glycol monopropylamineether containing acid oils, aromatics and other materials extracted fromthe gas oil feed is withdrawn from contacting zone 2 through line 9 andpassed into settling zone 10. Water and solvent from line *8 are alsointroduced into the settling zone. Dilution of the extract phase insettling zone 10 by the wash water introduced through line 8 results ina decreased solubility for aromatic hydrocarbons. Separate aromatic andaqueous solvent phases are therefore formed within the settling zone. Itis preferred that the amount of wash water employed in vessel 5constitute about 25% of the volume of the extract phase withdrawn fromthe contacting vessel 2. Dilution of the extract phase to this extentwill result in the separation of essentially all of the aromatics fromthe extract. These aromatics are withdrawn from the settling zonethrough line 11 and may subsequently be employed as a fuel constituent,as a solvent base, as a starting material for the manufacture ofchemicals or in other applications. Acid oils present in the extractphase remain in the aqueous solvent and therefore the aromaticswithdrawn through line 11 have a substantially better odor than did thefeed gas oil. This improvement in odor is of great importance if thearomatics are to be used as a fuel constituent or as a solvent base.

The aqueous monoethylene glycol monopropylamine layer formed in settlingzone 10 is withdrawn from the bottom of the zone through line 12 andintroduced into the coil of furnace 13 where it is heated to atemperature of about 350 F. The heated solution is then introduced bymeans of line 14 into atmospheric distillation column 15. In column 15water is flashed from the solvent and taken overhead through line 16.The ethylene glycol monopropylamine, which has a boiling point of about450 F.,, is withdrawn from the" distillation column in an anhydrousstate through line 17. The

major portion of this anhydrous solvent is recycled through line 18 andreintroduced into contacting zone 2. In order to maintain the acid oilscontent of the solvent at an acceptable level, however, a minorproportion of the anhydrous solvent, about for example, is taken offfrom line 17 through line 19 and introduced at a temperature of about320 F. into vacuum tower 20. Tower 20 is operated at a pressure of about50 mm. of mercury. At this pressure and temperature the monoethyleneglycol monopropylamine ether is vaporized and taken overhead throughline 21. The overhead stream is condensed in condenser 22 and thecondensate is passed through line 23 into line 18 through which it isrecycled. Acid oils are withdrawn from vacuum tower 20 as a bottomsproduct through line 24. This stream may be subsequently separated intophenols, thiophenols, cresols, xylenols and the like by known methodsand employed for a variety of purposes.

It will be understood that a number of modifications may be-made in theprocess described above without departing from the scope of the presentinvention. In lieu of using an anhydrous solvent, for example, anaqueous solvent containing from about 1 to about 50% water may becontacted with the feed stream at a temperature of from about 150 toabout 300 F. Upon separation of the extract and ratfinate phases formedin this contacting step, the extract layer may be cooled to reduce thesolubility for aromatics and precipitate an aromatics layer in thesettling zone. The solvent freed of aromatics may then be processed inthe manner described above in order to separate out the acid oils. Bycontrolling the contacting temperature and water content of the solventas discussed heretofore, the process may also be carried out so thatsubstantially no aromatic hydrocarbons will be extracted from thedistillate treated. Other modifications of the process described abovemay also be employed and will be obvious to those skilled in the art.

The process of the present invention may be still further illustrated byreference to the following examples.

EXAMPLE 1 A light cracked gas oil boiling between 376 and 638 F. wasextracted with anhydrous monoethylene glycol 6 90% 606 95% 620 FBP, -F638 Contacting of this gas oil with ethylene glycolmonopropylamine etherwas carried out in a single-stage batch extraction vessel. A 1 to 1solvent-to-feed ratio was used and the contacting temperature was 80 F.Upon separation of the extract and rafiinate phases formed and removalof solvent from these phases, it was found that 9 vol. percent of thefeed gas oil had been carried into the extract phase. The rafiinatephase, after removal of the solvent, contained 91 vol. percent of thefeed and was found to be essentially free of acid oils, pyrrolenitrogenand mercaptan sulfur.

EXAMPLE 2 In order to compare the results obtained in the precedingexample with those obtained when conventional solvents are used, anuntreated sample of the same gas oil treated in Example 1 was extractedwith diethylene glycol. The conditions employed were the same as thosein Example 1 except that a solvent-to-oil ratio of 2 to l was used.Despite this use of twice as much of the diethylene glycol as of themonoethylene glycol mono-v propylamine ether, it was found that thediethylene glycol did not extract any more of the aromatics from thefeed than did the monoethylene glycol monopropylamine ether. Therelative volumes of raffinate and extract recovered were essentially thesame as in the former case, 90% and 10% respectively. It thus appearsthat the monoethylene glycol monopropylamine ether has about .the sameselectivity for aromatics as does diethylene glycol but that thecapacity of the former is nearly twice that of the. conventionalsolvent. This surprisingly high capacity constitutes an importantadvantage for the monoethylene glycol monopropylamine ether overconventional solvents. In addition, it was found that the acid oilscontent of the diethylene glycol: treated rafiinate was not appreciablychanged and that the raffinate was not doctor pass, indicating thatdiethylene glycol does not possess the selectivity for acid oils andsulfur compounds which distinguishes the solvents of the invention.

nionopropylamine ether in accordance With the inven- EXAMPLE 3 tion.Inspections of the gas oil were as follows: I C b 9 2 The hydrocarbonsrecovered from the rafiinate phases F i in the preceding examples andthe hydrocarbon phase g 9 Per t a 8 obtained by caustic washing of asample of the same S f percen 39 gas oil were tested for their coppernumber, their aroa um es matics content and their odor. The odor testwas carried ASTM Distillation: out by a 40 member panel and each samplewas givena :IBP, F 376 rating based upon an arbitrary scale. Thedifference in 5% 440 rating necessary for significance was determinedstatis- 10% 458 tically. The results of these tests and similar testsupon 50% 530 the untreated gas oil are shown in the following table.

. IMPROVEMENT COPPER N0. AND ODOR BY TREATMENT WITH Y SOLVENTS Odor TestCopper Aromat- No. (Poics, V01. Samples tentio- Percent Necessarymetric) Aver. Difference Rating Score for Signifisauce 1 DiethyleneGlycol Treated on-.- 6.7 48 -0.3a ---"3.'d Caustic Treated Oil 2 53+0.08 0.31 1st Untreated Oil 9.2 53 +0.28 "1st Monoethylene GlycolMonopropyl amine Ether, Treated Oil 01 49. 5 +0. 1st Caustic Treated Oil2 53 -0.36 '0. 20 "2nd Untreated Oil 9.2 53 -0.39 2nd At confidencelevel. 0.1 is limit of accuracy of test.

From the above table it can be seen that the hydrocarbons obtained bytreatment of a gas oil with monoethylene glycol monopropylamine etherhad a copper number of less than 0.1, as compared to a copper number of6.7 for the diethylene glycol treated sample, a copper number of 2 forthe caustic treated sample and a copper number of 9.2 for the originalgas oil. This difference in copper number is significant and clearlyindicates that the process of the invention results in a product whichis much less corrosive than that obtained in conventional extractionprocesses. The odor test results show that caustic treating andtreatment with diethylene glycol produced a product having an odorlittle or no better than that of the untreated oil. Extraction with themonoethylene glycol monopropylamine ether, however, resulted in anappreciable improvement in odor. Since the aromatics contents of all ofthe samples were about the same, it is apparent that the odorimprovement obtained by use of the solvent of the invention was dueprimarily to a more complete extraction of acid oils rather than duemerely to the removal of aromatic hydrocarbons.

EXAMPLE 4 The extract phase obtained by treating a gas oil boilingbetween 412 F. and 656 F. with anhydrous monoethylene glycolmonopropylamine ether as in Example 1 was diluted with about 25 volumepercent water in order to separate out the hydrocarbons containedtherein. This hydrocarbon phase was recovered and analyzed. It was foundthat the hydrocarbons in the extract consisted of about 95% aromatics,were free of thiophenols, and contained only traces of phenols. Thisfraction is an excellent solvent for DDT and similar materials requiringhigh aromatic solvents and thus forms an attractive by-product of theprocess of the invention.

EXAMPLE 5 Samples of a heavy catalytically cracked naphtha boilingbetween 350 F. and 433 F. were treated with aqueous solutions ofdiethylene glycol monopropylamine ether containing from to 30% water byweight. Contacting of the solvent solutions and naphtha was carried outin single stage extraction vessels at temperatures of from 80 to 150 F.and with solvent to feed ratios of from 0.25:1 to 1:1. The acid oilscontents of the treated samples were then determined by ultra violetabsorption and compared with that of the untreated naphtha. Alkylatedphenols, cresols, xylenols and the like were reported together asphenols, while thiophenols were reported separately. A sample treatedwith diethylene glycol monopropylamine which had been regenerated byvacuum distillation was also tested. The results of these tests areshown in Table 11 below.

ranged between 63 and 96% and that thiophenols were completely removedfrom the naphtha in every case. The regenerated solvent showedessentially the same aflinity for acid oils as did the fresh solventunder the same treating conditions. The data in the table also show thatincreasing the contacting temperature does not improve the extraction ofacid oils from naphtha and instead results in a slightly decreasedaffinity of the aqueous solvents for acid oils. Increases in temperaturedo increase the aflinity of the solvents for aromatic hydrocarbons. Itshould be understood, however, that acid oils are extracted by thesolvents in preference to aromatics regardless of the conditionsemployed and that aromatics in the extract can therefore be controlledas desired without affecting the selective removal of acid oils. Insingle batch treats using a solvent-to-feed ratio of 0.5:1 and atemperature of 80 F. it has been found that the arcmatics content of theextract, based upon the feed, will range from about 10 vol. percent whenanhydrous diethylene glycol monopropylamine ether is used to about 0.5vol. percent or less when a solution of diethylene glycolmonopropylamine ether containing 30% water by volume is used. The datain Table II also illustrate the efiect of solvent-to-feed ratio in usingthe solvents for the removal of acid oils.

EXAMPLE 6 Table III REMOVAL or NITROGEN FROM NAPHTHA Total NitrogenPyrrole Nitrogen Wt. Percent Optical Percent Percent Reduc- Density 1Reduction tion Naphtha A 0. 023 1 0. 092 Treated Naphtha A 0. 018 200.052 43 Naphtha B 3 0. 47 Treated Naphtha B 0. 31 34 1 Light absorptionof the color complex formed by pyrrole compounds with p-dimethylaminobenzaldehyde in phosphoric-acetic acid solution mgaizlarfdnalt 242mm. on a Beckman DU-Spectrophotometer.

: u ion.

8 20:1 dilution.

Table II REMOVAL OF PHENOLS AND THIOPHENOLS FROM NAPHTHA H O in PhenolsPhenols Thio- Thic- Solvent/ Solvent, 'lernp., Content, Reducphenolsphenols Treat Feed Wt. Per- F. Wt. Pertion, Content, Reduc- Ratio centcent Percent Wt. Per tion,

cent Percent 0.324 0.079 10 80 0. 037 89 Nil 100 10 80 0.015 96 Nil 10020 80 0.082 Nil 100 30 0.090 71 Nil 30 80 0. 037 89 Nil 100 30 80 0.03091 N11 100 30 0. 104 68 Nil 100 30 0. 120 63 Nil 100 I (Regen.

Solvent) 1/1 30 80 0.040 88 Nil 100 From the above table it can be seenthat the reduc- As shown by the above data, the treatment of petion inphenols, cresols and xylenols, expressed as phenols, 75 troleumdistillates with ethylene glycol monoalkylamine 9. ethers in accordancewith the invention removes nitrogen compounds, as well as acid oils,from the distillates treated. This removal of nitrogen compounds is ofimportance, since it is known that such compounds promote the formationof sludge in gasolines and many other petroleum distillate products.

EXAMPLE 7 A cracked naphtha containing 29 milligrams of mercaptan sulfurper 100 milliliters was treated with a 50 volume percent treat of anaqueous diethylene glycol monopropylamine ether solution containing 30weight percent water. Analysis of the extract and raflinate phasesshowed that the raflinate contained only 0.1 milligrams of mercaptansulfur per 100 milliliters and that the extract contained 62 milligramsper 100 milliliter. The treated distillate was thus considerably betterthan Doctor Pass, about 0.5 milligrams per 100 milliliters by thepotentiometric copper number method employed. The effectiveness of thesolvents for sweetening cracked distillates as well as for removing acidoils from such distillates is thus further demonstrated.

EXAMPLE 8 A spent solution of aqueous diethylene glycol monopropylamineether was regenerated by vacuum distillation to remove water, acid oils,and high boiling materials accumulated therein as a result of extendeduse. Comparative inspections of the fresh and regenerated anhydrousdiethylene glycol monopropylamine ether are shown in Table IV.

Table I V INSPECTIONS OF FRESH AND REGENERATED SOLVENT No. of NH: Sp.Gr. Mer- Groups Per R1. at 77 F. oaptan olecule Sulfur Fresh Solvent 1.02 1. 4653 1.051 Nil Regenerated Solvent 1. O4 1. 4662 1. 050 0.6

where x is a digit from 1 to 4 inclusive and y is a digit from 1 to 5inclusive.

2. A process as defined by claim 1 wherein said ether is a monoethyleneglycol monoalkylamine ether.

3. A process as defined by claim 1 wherein said ether is a polyethyleneglycol monoalkylamine ether.

4. A process as defined by claim 1 wherein said distillate is contactedwith said ether at a temperature in the range of from about 60 to about300 F.

5. A process as defined by claim 1 wherein said ether is anhydrous.

6. A process as defined by claim 1 wherein said ether contains fromabout 1 to about 50% water.

7. A process as defined by claim 1 wherein said distillate is contactedwith from about 0.1 to about 5 volumes of said ether per volume ofdistillate.

8. A process as defined by claim 1 wherein said distillate is a crackeddistillate.

9. A process as defined by claim 1 wherein said ether is monoethyleneglycol monopropylamine ether.

10. A process as defined by claim 1 wherein said other is diethyleneglycol monopropylamine ether.

11. An improved process for removing acid oils from a petroleumdistillate boiling between about F. and about 900 F. which comprisescontacting said distillate, at a temperature of from about 60 to about300 F. and under conditions to form separate rafiinate phases, with fromabout 0.1 to about 5 volumes of an ethylene glycol monoalkylamrine etherhaving the formula where x is a digit from 1 to 4 inclusive and y is adigit from 1 to 5 inclusive; separating said phases; recovering ahydrocarbon fraction of substantially reduced acid oils content fromsaid raffinate phase; and recovering acid oils from said extract phase.

12. A process as defined by claim 11 wherein said distillate iscontacted with from about 0.5 to about 2 volumes of said ether pervolume of distillate.

13. A process as defined by claim 11 wherein said distillate is acracked distillate.

14. A process as defined by claim 11 wherein said distillate iscontacted with said ether at a temperature between about 60 and about F.

15. A process as defined by claim 11 wherein said distillate iscontacted with an anhydrous solution of said ether and a highly aromatichydrocarbon fraction is recovered from the extract phase.

16. A process as defined by claim 11 wherein said distillate iscontacted with an aqueous solution of said ether containing from about 1to about 50% water.

17. A process as defined by claim 11 wherein.- said ether ismonoethylene glycol monopropylamine ether.

18. A process as defined by claim 11 wherein said ether is diethyleneglycol monopropylamine ether.

19. A process as defined by claim 11 wherein said ether is triethyleneglycol monobutylamine ether.

20. A process for removing acid oils from a cracked petroleum naphthaboiling above about 200 F. which comprises treating the same with anaqueous solution of a polyethylene glycol monoalkylamine ethercontaining from 7 to 13 carbon atoms per molecule in the absence ofsubstantial quantities of caustic.

21. A process for the removal of alkylated phenols, cresols, xylenolsand thiophenols from a cracked petroleum fraction boiling between about200 F. and about 430 F. which comprises contacting said fraction with anaqueous solution of a polyethylene glycol monoalkylamine ethercontaining from 7 to 13 carbon atoms per molecule in the absence ofsubstantial quantities of caustic.

22. A process in accordance with claim 21 wherein said aqueous solutioncontains from 50 to 90% by volume of polyethylene glycol monoalkylamineether.

23. A process in accordance with claim 22 wherein said polyethyleneglycol monoalkylarnine ether is diethylene glycol monopropylamine ether.

24. A process in accordance with claim 23 wherein said petroleumfraction boils in the range between about 300 F. and about 430 F.

25. A process for the extraction of acid oils from a cracked petroleumnaphtha boiling in the range between about 200 F. and about 430 P. whichcomprises contacting said naphtha in the absence of substantialquantities of caustic with an aqueous solution of diethylene glycolmonopropylamine ether containing from 50 to 90% by volume of said etherunder conditions to form an extract phase and a raffinate phase,separating said phases, and recovering substantially acid oils-freenaphtha from said rafiinate phase.

26. A process in accordance with claim 25 wherein said naphtha fractionis contacted with said aqueous solution at a tempearture in the rangebetween about 60 F. and to about 1 volume of said aqueous solution pervolume about 15 0 F. of naphtha.

.27. A process in accordance with claim 26 wherein said naphtha fractionis a catalytically cracked fraction References Clted 1n the file of thisP boiling in the range between about 300 F. and about 5 UNITED STAT SPATENTS 430 F.

28. A process in accordance with claim 27 wherein figfi ggf a1 g saidnaphtha fraction is contacted with from about A

1. AN IMPROVED PROCESS FOR REMOVING ACID OILS FROM A PETROLEUMDISTILLATE BOILING BETWEEN ABOUT 100* F. AND ABOUT 900* F. WHICHCOMPRISES CONTACTING SAID DISTILLATE WITH AN ETHYLENE GLYCOLMONOALKYLAMINE ETHER HAVING THE FORMULA